CN109108279A - A kind of poly-dopamine coated copper nanowire composite and its preparation method and application - Google Patents
A kind of poly-dopamine coated copper nanowire composite and its preparation method and application Download PDFInfo
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- CN109108279A CN109108279A CN201811065159.6A CN201811065159A CN109108279A CN 109108279 A CN109108279 A CN 109108279A CN 201811065159 A CN201811065159 A CN 201811065159A CN 109108279 A CN109108279 A CN 109108279A
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- Prior art keywords
- polydopamine
- coated copper
- composite material
- nanowire composite
- copper nanowire
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- 239000010949 copper Substances 0.000 title claims abstract description 77
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 69
- 239000002070 nanowire Substances 0.000 title claims abstract description 63
- 229920001690 polydopamine Polymers 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 39
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000011065 in-situ storage Methods 0.000 claims abstract description 8
- 229960003638 dopamine Drugs 0.000 claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 5
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- 230000001590 oxidative effect Effects 0.000 claims abstract 4
- 239000000243 solution Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 8
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 7
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 6
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 5
- 239000004917 carbon fiber Substances 0.000 claims description 5
- 239000011736 potassium bicarbonate Substances 0.000 claims description 5
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000007853 buffer solution Substances 0.000 claims description 4
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- 239000011545 carbonate/bicarbonate buffer Substances 0.000 claims description 2
- 229910021397 glassy carbon Inorganic materials 0.000 claims 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical class OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 238000011946 reduction process Methods 0.000 abstract 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 8
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 229960001149 dopamine hydrochloride Drugs 0.000 description 3
- 238000001548 drop coating Methods 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- -1 hydrogen Salt Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical compound [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/102—Metallic powder coated with organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/095—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one of the compounds being organic
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种聚多巴胺包覆铜纳米线复合材料及其制备方法和应用。聚多巴胺包覆铜纳米线复合材料由聚多巴胺包覆铜纳米线构成；其制备方法是利用多巴胺的原位氧化聚合包覆在铜纳米线表面得到；聚多巴胺包覆铜纳米线复合材料应用在电催化CO2还原过程中不但可以提高甲烷选择性而且表现出高稳定性。The invention discloses a polydopamine-coated copper nanowire composite material and a preparation method and application thereof. The polydopamine-coated copper nanowire composite material is composed of polydopamine-coated copper nanowires; the preparation method is obtained by coating the surface of copper nanowires by in-situ oxidative polymerization of dopamine; the polydopamine-coated copper nanowire composite material is applied in The electrocatalytic CO reduction process can not only improve the methane selectivity but also show high stability.
Description
Technical field
The present invention relates to a kind of CO2RR catalyst, and in particular to a kind of poly-dopamine coated copper nanowire composite, also
It is related to it to receive by the method and poly-dopamine coated copper of in-situ polymerization preparation poly-dopamine coated copper nanowire composite
Rice noodles composite material is as CO2RR catalyst restores CO by electro-catalysis2The highly selective method for preparing methane, belongs to titanium dioxide
Carbon emission reduction utilizes and electrocatalysis material synthesizes and application field.
Background technique
A large amount of consumption due to industrial society to fossil fuels such as coal, oil and natural gas, it is uncontrolled to fossil fuel
Exploitation lead to the shortage of resource, and the burning of fossil fuel generates a large amount of CO2Aggravate greenhouse effects constantly.So will
CO2Being converted into renewable energy not only can solve greenhouse effects, but also energy alleviating energy crisis, equal to environment, the energy and economic three
It is of great significance.Electrochemical process restores CO2It is mild with reaction condition, reaction process is easily-controllable, and driven using clean energy resource
The advantages that dynamic, be the hot spot and application direction studied now.
Cu be recognized be uniquely being capable of efficient electro-catalysis CO2The metallic catalyst for generating complicated hydrocarbon, because forming
For the first choice of elctro-catalyst.But the deficiency of selectivity and stability becomes the key for hindering the practical application of Cu catalyst
Problem.
From CO2To methane (CO2+8H++8e-→CH4+2H2O electro-catalysis conversion) is that one kind has promising conversion very much
Path, the conversion will be from CO2Production natural gas provides a kind of completely new approach.In order to improve carbon dioxide having to methane
Conversion ratio is imitated, most of study is directed generally to design crystal face, optimizes carrier, control electrolysis mode and change electrolyte environment
Deng.Nevertheless, but from the perspective of elctro-catalyst, it is still difficult to solve CO2CH in RR4The low problem of selectivity.According to report
Road, amino acid modification Cu electrode realize C2Hydrocarbon (C2H4And C2H6) faradic efficiency improve.Therefore, organic molecule is functionalized
The whether adjustable CH of Cu electrode4Selectivity is still one very big challenge.In addition, according to existing studies have shown that due to quiet
Electric repulsion and thermodynamic phase, the Cu atom of Cu electrode surface are easy to lose atom and be recombinated in electro-catalysis, caused
Significant variation occurs for pattern and crystal, leads to the unstable of catalyst.
Summary of the invention
For copper in the prior art as CO2RR catalyst has that stability and methane selectively are insufficient, this hair
Bright purpose is to be to provide a kind of utilization chemical activity poly-dopamine package copper nano-wire composite material, which exists
CO2During RR catalyzed conversion methane, the features such as stability is good, and catalytic activity is high, and selectivity is good is shown.
Second object of the present invention is to be to provide a kind of easy to operate, inexpensive, and preparing for mild condition is described poly-
The method of dopamine coated copper nanowire composite.
Third object of the present invention is to be to provide the application of poly-dopamine coated copper nanowire composite, is made
For CO2RR catalyst application, passes through electro-catalysis CO2It is reduced into methane, shows selective height, the advantages that stability is good.
In order to achieve the above technical purposes, the present invention provides a kind of poly-dopamine coated copper nanowire composite,
It is made of poly-dopamine cladding copper nano-wire.
The present invention wraps up modification copper nano-wire using poly-dopamine, and poly-dopamine includes active group abundant, right
Copper nano-wire compatibility is preferable, and poly-dopamine can obtain stable clad structure on copper nano-wire surface.Poly-dopamine is repaired
Decorations can greatly improve the chemical stability and thermal stability of copper nano-wire, prevent copper nano-wire in electricity on copper nano-wire surface
Chemical change occurs in catalytic process and fails.In addition find that the group in poly-dopamine has the catalytic selectivity of copper nano-wire
It is obviously improved, carbon dioxide reduction (CO can be effectively improved2RR) in product methane selectivity.
The mass ratio of preferred scheme, poly-dopamine and copper nano-wire is 1:100~20:100.In preferred proportional region
It is interior, it is ensured that poly-dopamine obtains relatively uniform clad on copper nano-wire surface.
The present invention also provides a kind of preparation method of poly-dopamine coated copper nanowire composite, this method is by copper
Nano wire be dispersed in dopamine solution carry out in-situ oxidizing-polymerizing to get.
The mass ratio of preferred scheme, dopamine and copper nano-wire is 1:100~20:100.
Preferred scheme, the condition of the in-situ oxidizing-polymerizing: pH be 8.0~9.0, at normal temperature, oscillation or stand 8~
24 hours.
Preferred scheme, the in-situ oxidizing-polymerizing use carbonate/bicarbonate buffer solution or phosphate/phosphor acid hydrogen
Salt buffer solution adjusts pH.These preferred buffer solutions and copper are without complexing and corrosiveness.
The present invention also provides a kind of applications of poly-dopamine coated copper nanowire composite, as CO2RR is urged
Agent is applied to CO2RR is converted into methane.
Preferred scheme, to load the electrode of poly-dopamine coated copper nanowire composite as working electrode, Pt piece is
To electrode, Ag/AgCl electrode is reference electrode, forms three-electrode system, potassium bicarbonate solution is electrolyte, uses proton exchange membrane
Separate cathode chamber and anode chamber, continuously exposes in cathode chamber into CO2Gas carries out constant potential and restores CO2。
Preferred scheme, by poly-dopamine coated copper nanowire composite by coating method be supported on glass-carbon electrode or
Carbon fiber paper surface obtains the electrode of load poly-dopamine coated copper nanowire composite；It is multiple that poly-dopamine coats copper nano-wire
Condensation material is 0.25~2.5mg/cm in the load capacity of glass-carbon electrode or carbon fiber paper surface2.Coating method such as drop coating, spraying
Deng.
Preferred scheme, the constant potential restore CO2In the process, control of Electric potentials range is -1.6~-1.8V (Ag/
AgCl), the concentration of potassium bicarbonate solution is 0.3~0.7mol/L.
Copper nano-wire of the invention is referred to following methods and is prepared: taking 20mL 15M NaOH (98%), 1mL
0.1M Cu(NO3)2(98%), 0.1mL ethylenediamine (EDA, 99%) is in three-necked flask, and flask is placed on 70 DEG C of water-baths, while with
250rpm rate stirs 5min. then hydrazine hydrate (10.5 μ L, N2H4, 35wt.%in H2O), increase stirring rate to 2 times；Most
Whole Cu (NO3)2、EDA、N2H4Dosage is respectively 4.74mM, 70mM, 5.5mM.It is filtered after reaction 60min, by the palm fibre on filter membrane
The a large amount of 3%N of red solid2H4Obtained solid is placed in 60 DEG C of vacuum ovens 8h to get copper nano-wire by solution cleaning.
Poly-dopamine coated copper nanowire composite of the invention the preparation method is as follows: by the copper nano-wire of synthesis point
It dissipates in deionized water, by the way that the spontaneous carry out oxidation polymerization of Dopamine hydrochloride of different quality ratio is added and realizes to copper nano-wire
Package modification；The mass ratio of Dopamine hydrochloride and copper is 1:100~20:100, adjusts pH to 8.0~9.0, adjusts pH value of solution
Reagent be carbonate/bicarbonate, the buffer solution with copper without complexing and corrosiveness such as phosphate/phosphor acid hydrogen salt；
Then vibrating at normal temperature or standing 8~24 hours can be obtained poly-dopamine package modification copper nano-wire；
Poly-dopamine coated copper nanowire composite of the invention is used for CO2RR electro-catalysis is converted to the method for methane such as
Under: the electrode using load poly-dopamine coated copper nanowire composite is working electrode, is to electrode, Ag/ with Pt piece
AgCl electrode is reference electrode, forms three-electrode system；The poly-dopamine coated copper nanowire composite passes through drop coating, spray
The modes such as painting are fixed on glass-carbon electrode or carbon fiber paper, and load capacity is 0.25~2.5mg/cm2；Use potassium bicarbonate solution for
Electrolyte separates cathode chamber and anode chamber with proton exchange membrane, continuously exposes in cathode into CO2Constant potential restores under conditions of gas
CO2；In order to obtain higher CH4Selectivity, constant potential restore CO2Control of Electric potentials range be -1.6~-1.8V (Ag/AgCl),
The preferred concentration of electrolyte saleratus is 0.5mol/L.
Compared with prior art, technical solution of the present invention bring advantageous effects:
1) present invention wraps up modification copper nano-wire using poly-dopamine, and the chemical stabilization of copper nano-wire not only can be improved
Property and thermal stability, prevent copper nano-wire from chemical change occurs during electro-catalysis and fails, to keep the long-acting of catalyst
Stablize, and can use the group in poly-dopamine to improve the catalytic selectivity of copper nano-wire, carbon dioxide can be effectively improved
Restore (CO2RR) in product methane selectivity.
2) the relatively unmodified copper nano-wire material of poly-dopamine coated copper nanowire composite of the invention, is used for
CO2RR electro-catalysis is converted to methane, methane selectively can be improved 1.3 times or more under same potential, and can prolong significantly
The service life of long catalyst.
3) preparation method of the invention is simple, and reaction condition is mild, at low cost, is conducive to industrialized production.
Detailed description of the invention
[Fig. 1] is the materialization characterization of the copper nano-wire of the poly-dopamine coating decoration synthesized in embodiment 1；(a)XRD；(b)
HRTEM；(c) linear EDS (b figure line strip area).
[Fig. 2] is the corresponding CO of CuNWs@PDA of different Jacket thickness in embodiment 12Reduzate selectivity.
[Fig. 3] is the copper nano-wire of the modification of poly-dopamine difference Jacket thickness and the copper nanometer that do not wrap up in embodiment 1
The catalytic stability of line compares.
Specific embodiment
It is intended to further illustrate the present invention with reference to embodiments, not the limitation present invention.Present inventive concept is not being departed from
Under the premise of make it is corresponding adjustment and improve, belong to protection scope of the present invention.
Embodiment 1
1) synthesis of poly-dopamine package modification copper nano-wire:
Take 20mL 15M NaOH (98%), 1mL 0.1M Cu (NO3)2(98%), 0.1mL ethylenediamine (EDA, 99%) in
Three-necked flask, flask are placed on 70 DEG C of water-baths, while with 250rpm rate stirring 5min. and then hydrazine hydrate (10.5 μ l, N2H4,
35wt.%in H2), O increase the stirring rate Cu (NO final to 2 times of3)2,EDA,N2H4Dosage is respectively 4.74mM, 70mM,
It is filtered after 5.5mM. reaction 60min, by the brown-red solid on filter membrane with a large amount of 3%N2H4Solution cleaning, obtained solid is placed in
8h in 60 DEG C of vacuum ovens.By suitable Dopamine hydrochloride (1.2mg, 2.5mg, 5.0mg, 10mg) be dissolved in 100mL go from
In sub- water, KHCO is used3/K2CO3Solution adjusts pH value of solution to 8.5.50mg copper nano-wire is weighed, ultrasonic disperse is in the above solution.
Then the conical flask equipped with the above solution is placed in shaking table, 220r/min vibrates for 24 hours.Filtering, cleaning, finally set gained sample
In 60 DEG C of vacuum drying ovens, dry 8h.In conjunction with Fig. 1's as a result, obviously having wrapped up one layer of polymer containing C, N, O on copper nano-wire
(PDA)。
2)CO2Electroreduction test:
The above-mentioned material of 5mg synthesis is weighed in centrifuge tube, 500ul water and 500ul dehydrated alcohol is added, continuously adds
The catalyst dispersion homogeneously dispersed is made after ultrasonic disperse for 40ul Nafion solution (5%w/w).Then by 50ul or more points
The uniform drop coating of dispersion liquid (load capacity 0.25mg/cm on the glass-carbon electrode of 1 × 1cm2), air-dry stand-by, obtained working electrode.Make
With the closed electrolytic cell of H-type, cathode chamber and anode chamber are separated using N117 proton exchange membrane, using 2 × 2cm platinum plate electrode as
To electrode, Ag/AgCl electrode is as reference electrode.Electrolyte is 0.5mol/l KHCO3Solution, by CO2Gas is passed through cathode chamber
Make electrolyte CO2Saturation, makes CO in electrolyte2It is fully saturated.CO is carried out with potentiostatic deposition mode2Reduction, potential setting be-
1.6V(Ag/AgCl)。
In electrolytic process, by the catalytic current on electrochemical workstation recording electrode, using gas-chromatography to CO2Also
Former gas-phase product carries out on-line determination.After being electrolysed 3h, gaseous product concentration and electrolysis institute's power consumption are surveyed according to GC, obtain each gas
The faradic efficiency of phase product.In conjunction with Fig. 2's as a result, CuNWs@PDA improves the selectivity of CH4, and can be according to the packet of PDA
The amount of wrapping up in carries out Effective Regulation；Illustrate CuNWs@PDA after package in conjunction with the result of Fig. 3, the great improvement that stability obtains.
Claims (10)
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111215146A (en) * | 2020-02-17 | 2020-06-02 | 中南大学 | A kind of group-modified noble metal-based carbon dioxide electroreduction catalyst, preparation method and application thereof |
| CN111701611A (en) * | 2020-04-13 | 2020-09-25 | 南京工业大学 | A kind of bivalent copper carbon dioxide reduction catalyst based on carbonate synergy and preparation method thereof |
| CN111827000A (en) * | 2020-08-04 | 2020-10-27 | 济南大学 | A copper composite conductive paper based on multi-site catalytic in-situ reduction technology |
| CN113235127A (en) * | 2021-04-21 | 2021-08-10 | 北京航天动力研究所 | Carbon interlayer copper nanosheet electrocatalyst with sandwich structure, preparation method, electrode and application |
| CN113857473A (en) * | 2021-09-28 | 2021-12-31 | 南方电网电力科技股份有限公司 | Copper nanowire material and preparation method and application thereof |
| CN115094480A (en) * | 2022-06-08 | 2022-09-23 | 上海交通大学 | Synthetic method and application of azulene-based polymer-copper particle composite material |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150295106A1 (en) * | 2014-04-09 | 2015-10-15 | Walter J. Dressick | Method for fabrication of copper-indium gallium oxide and chalcogenide thin films |
| CN105602201A (en) * | 2016-03-21 | 2016-05-25 | 西南科技大学 | Preparation method of high-strength conductive polymer nanocomposite |
| CN105680021A (en) * | 2016-03-26 | 2016-06-15 | 上海大学 | Poly-dopamine coated nano-micro powder and preparation method thereof |
| CN107020389A (en) * | 2017-04-06 | 2017-08-08 | 江苏大学 | A kind of preparation method of high-dispersion nano copper |
| CN107096916A (en) * | 2017-05-14 | 2017-08-29 | 蒋春霞 | A kind of preparation method of silver-coated copper powder |
| CN107841760A (en) * | 2016-09-19 | 2018-03-27 | 中国科学院大连化学物理研究所 | Electrochemical reduction CO2The gas-diffusion electrode preparation method of hydrocarbon processed |
| CN107976431A (en) * | 2017-11-23 | 2018-05-01 | 深圳大学 | Surface enhanced Raman substrate based on metal nanoparticle and preparation method thereof |
-
2018
- 2018-09-13 CN CN201811065159.6A patent/CN109108279B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150295106A1 (en) * | 2014-04-09 | 2015-10-15 | Walter J. Dressick | Method for fabrication of copper-indium gallium oxide and chalcogenide thin films |
| CN105602201A (en) * | 2016-03-21 | 2016-05-25 | 西南科技大学 | Preparation method of high-strength conductive polymer nanocomposite |
| CN105680021A (en) * | 2016-03-26 | 2016-06-15 | 上海大学 | Poly-dopamine coated nano-micro powder and preparation method thereof |
| CN107841760A (en) * | 2016-09-19 | 2018-03-27 | 中国科学院大连化学物理研究所 | Electrochemical reduction CO2The gas-diffusion electrode preparation method of hydrocarbon processed |
| CN107020389A (en) * | 2017-04-06 | 2017-08-08 | 江苏大学 | A kind of preparation method of high-dispersion nano copper |
| CN107096916A (en) * | 2017-05-14 | 2017-08-29 | 蒋春霞 | A kind of preparation method of silver-coated copper powder |
| CN107976431A (en) * | 2017-11-23 | 2018-05-01 | 深圳大学 | Surface enhanced Raman substrate based on metal nanoparticle and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 黄鹏、许江伟: "铁掺杂铜纳米花用于电化学还原 CO2", 《江西化工》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111215146A (en) * | 2020-02-17 | 2020-06-02 | 中南大学 | A kind of group-modified noble metal-based carbon dioxide electroreduction catalyst, preparation method and application thereof |
| CN111701611A (en) * | 2020-04-13 | 2020-09-25 | 南京工业大学 | A kind of bivalent copper carbon dioxide reduction catalyst based on carbonate synergy and preparation method thereof |
| CN111827000A (en) * | 2020-08-04 | 2020-10-27 | 济南大学 | A copper composite conductive paper based on multi-site catalytic in-situ reduction technology |
| CN113235127A (en) * | 2021-04-21 | 2021-08-10 | 北京航天动力研究所 | Carbon interlayer copper nanosheet electrocatalyst with sandwich structure, preparation method, electrode and application |
| CN113857473A (en) * | 2021-09-28 | 2021-12-31 | 南方电网电力科技股份有限公司 | Copper nanowire material and preparation method and application thereof |
| CN115094480A (en) * | 2022-06-08 | 2022-09-23 | 上海交通大学 | Synthetic method and application of azulene-based polymer-copper particle composite material |
| CN115094480B (en) * | 2022-06-08 | 2023-09-12 | 上海交通大学 | Synthesis method and application of azulene-based polymer-copper particle composite material |
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